Suppression of aqueous viscosity of nonionic associative thickeners

ABSTRACT

A composition is composed of a hydrophobically modified aminoplast polyether or hydrophobically modified non-urethane polyethers with a viscosity suppressing agent of cyclodextrins or derivatives thereof. A method for improving the pumpability and pourability of aqueous solutions of thickener of a hydrophobically modified aminoplast polyether or hydrophobically modified non-urethane polyethers which is provided by admixing a cyclodextrin with the thickener to form a complex of the cyclodextrin and thickener where the viscosity of the thickener is suppressed and adding the complexed admixture to an aqueous system containing a water-insoluble polymer wherein the cyclodextrin is decomplexed and the thickener becomes an effective thickener. An example of the uses for this composition and method is in film forming coatings such as latex paints.

FIELD OF INVENTION

[0001] This invention relates to controlling the solution viscosity andother rheological properties of associative thickeners in aqueous media.More particularly, this invention relates to controlling the viscosityof high solids solution of aminoplast-polyether and non-urethaneassociative thickeners.

BACKGROUND OF THE INVENTION

[0002] Highly filled aqueous systems, such as water-borne coatings(latex or emulsion paints), inks, construction materials, and cosmeticsare formulated with hydrophobically modified water-soluble polymers(HM-WSPs) to control the rheology of coatings during manufacturing,storage and applications. These HM-WSPs are commonly referred to in theart as “associative thickeners”. They are so called because they thickenthe latex paints by forming a three-dimensional network throughintermolecular associations of the hydrophobic moieties present in theHM-WSP chains and/or with other hydrophobic components present in thecoatings formulation. Water-borne architectural coatings are used foron-site application to interior or exterior surfaces of residential,commercial, institutional, or industrial buildings. Associativethickeners have become the industry standards as the rheology modifiersin paints because they have a number of advantages over conventionalthickener systems. These include: (1) a lower viscosity duringincorporation, (2) a lower tendency to spatter during application, (3)good flow and leveling upon application, (4) better color, (5) highergloss through less flocculation, (6) lower sensitivity of the coatingsto water, (7) less vulnerability to microbial degradation, and (8)minimal reduction in the viscosity of the thickened dispersions onexposure to shearing (approaching Newtonian flow behavior).

[0003] These associative thickeners pose considerable difficulties todisperse or dissolve them in water or rapidly incorporate them intowaterborne coatings formulations. When the powder form of thesethickeners is added directly into a waterborne coating formulation, forexample, latex paint, they form lumps or globules and do not completelydissolve even after mixing for a long time. This behavior of thesethickeners is undesirable for coatings manufacturing as their thickenersslow down the manufacturing process. To eliminate these problems, thesethickeners are sold as high solids solutions in water or in a mixture ofwater and an organic co-solvent, such as butyl carbitol or propyleneglycol. The function of these organic co-solvents is to suppress theviscosity of the aqueous solution containing the associative thickenerto allow for ease of handling before it is used as a thickener. Whilethese organic co-solvents perform their intended function, they possesspotential environmental, safety, and health problems. These organicco-solvents contribute to volatile organic compounds (VOCs) which arenot environmentally friendly. Since these VOCs potentially harm theatmosphere, environmentalists are getting bills passed in the Governmentin order to reduce the VOCs emitted into the atmosphere. Hence,companies that produce or market formulations that produce large volumesof VOCs are being required either to reduce the level of VOCs or toeliminate them all together. Companies in the paint industry are nowconcerned about VOCs and are asking their raw materials suppliers toprovide environmentally friendly products with low or no VOCs.

[0004] One approach to suppress the aqueous viscosity of associativethickeners and yet be environmentally friendly is to use surfactants inthe paint. Although this presents no specific health or environmentalhazard, it does degrade formulation performance. U.S. Pat. No. 5,425,806, 6,020,407 (issued to Rheox, Inc.) and 6,150,445 (issued to AkzoNobel AV) describe the use of surfactants, which owing to theirmicelle-forming capability can reduce the viscosity of the aqueousconcentrate of the associative thickener.

[0005] Another approach is described in U.S. Pat. Nos. 5,137,571 and5,376,709 that disclose the use of cyclodextrins or their derivatives tosuppress the solution viscosity of hydrophobically modified ethoxylatedpolyurethanes, hydrophobically modified alkali-soluble emulsions,hydrophobically modified hydroxyethylcellulose, or hydrophobicallymodified polyacrylamides.

[0006] U.S. Pat. Nos. 5,916,935 and 6,057,398 describes the preparationof a concentrated solution of thickeners by forming an admixture of anon-urethane associative thickener compound and surfactants inconjunction with water and an organic solvent and subsequentlyazeotropically distilling off the organic solvent. The associativethickener solution thus obtained is typically essentially free of VOCs.

[0007] Another approach is to reduce the molecular weight of theassociative thickener so that no viscosity suppressant is needed toprepare high solids solutions in water with manageable viscosity.

[0008] Recently, the compositions and applications of a new class ofassociative thickeners based on hydrophobically modified poly(acetal- orketal-polyether) were described in U.S. Pat. Nos. 5,574,127 and6,162,877. Compared to many existing associative thickeners (see U.S.Pat. No. 5,574,127), these polymers were useful as rheology modifiersfor highly filled aqueous systems at very high pHs to provide thedesired properties. However, like many high molecular weight associativethickeners, these polymers exhibit high viscosity at high solidssolutions in water. Consequently, their use in many commercialapplications is restricted. U.S. patent application Ser. No. 10/003,755(DKT 10047), filed Oct. 29, 2001 describes the suppression of thesolution viscosity of hydrophobically modified poly(acetal- orketal-polyethers) with cyclodextrins.

[0009] Therefore, to widen the utility of these associative thickeners,it is desirable to develop means to lower their high solids solutionviscosity. The present invention is directed to address this issue withother commercial synthetic associative thickeners having differentchemical compositions.

SUMMARY OF THE INVENTION

[0010] The present invention is directed to a composition comprising anaqueous solution of a) a hydrophobically modified aminoplast-polyetheror non-urethane polyether and b) a viscosity suppressing agent selectedfrom cyclodextrins and derivatives thereof.

[0011] This invention also relates to a method for improving thepumpability and pourability of aqueous solutions of an associativethickener selected from the group consisting of hydrophobically modifiedaminoplast-polyethers described in U.S. Pat. Nos. 5,627,232, 5,629373,5,914,373 (issued to United Catalysts, Inc.), WO 01/12712 (applied bySud-Chemie, Inc.) and nonurethane polyether thickeners described in U.S.Pat. Nos. 4,288,639, 4,354,956, 4,411,819, 4,673,518, 4,649,224,4,904,466 (issued to BASF Corporation) and U.S. Pat. Nos. 5,728, 895,5,880,222, 5,916,935, & 6,057,388 (issued to Henkel Corporation)comprising admixing a cyclodextrin with the associative thickener toform a complex of the associative thickener where the viscosity of theassociative thickener is suppressed and adding the complexed admixtureto an aqueous system containing a water-insoluble polymer wherein thecyclodextrin is decomplexed and the associative thickener becomes aneffective thickener.

DETAILED DESCRIPTION OF THE INVENTION

[0012] It has been surprisingly found that blends of a hydrophobicallymodified aminoplast-polyether described in U.S. Pat. Nos. 5,627,232,5,629,373, 5,914,373 and WO 01/12712 or non-urethane polyetherthickeners described in U.S. Pat. Nos. 4,288,639, 4,354,956, 4,354,956,4,411,819, 4,673,518, 4,904,466, 5,728,895, 5,880,222, 5,916,935, and6,057,388 and cyclodextrin can make a high solids, low viscosity blendthat when added to an aqueous medium can form pumpable and pourableslurries or solutions at low water concentrations all the way up tosubstantially clear homogeneous solutions at medium to high waterconcentrations.

[0013] The polymers of this invention are substantially completelysoluble in water at ambient temperatures and have been found toefficiently thicken various water-based systems including latex paints.They also provide an improved combination of paint properties(stability, flow and leveling, film build, spatter resistance, and sagresistance). These polymers described in U.S. Pat. Nos. 4,288,639,4,354,956, 4,354,956, 4,411,819, 4,673,518, 4,904,466, 5,728, 895,5,880,222, 5,916,935, and 6,057,388 are associative thickeners thateither have a backbone of aminoplast-polyether or polyether with endsthat are capped with hydrophobic groups.

[0014] The preparations of various hydrophobically modified aminoplastpolyethers associated with the present invention are described in U.S.Pat. Nos. 5,627,232, 5,629,373, 5,914,373 and WO 01/12712 and theirdisclosures are herein incorporated by reference.

[0015] The preparations of various non-urethane thickeners associatedwith the present invention are described in U.S. Pat. Nos. 4,288,639,4,354,956, 4,354,956, 4,411,819, 4,673,518, 4,904,466, 5,728, 895,5,880,222, 5,916,935, and 6,057,388 12712 and their disclosures areherein incorporated by reference.

[0016] Cyclodextrins (CDs) are cyclic oligosaccharides with six totwelve alpha-D-anhydroglucose units connected together by alpha-(1,4)linkages. They are well known in the art and commercially available. Thecyclodextrins composed of six, seven and eight anhydroglucose rings arereferred to as alpha (α)-, beta (β)- and gamma (γ)-cyclodextrinrespectively. These truncated cone-shaped molecules are characterized byhaving a hydrophobic cavity and a relatively hydrophilic exterior. Oneof the unique properties of CDs is their ability to include appropriatehydrophobic compounds in their cavity to form host-guest complexes.

[0017] Cyclodextrins are produced from starch of any selected plantvariety, such as corn, potato, waxy maize, and the like which may bemodified or unmodified starch derived from cereal or tuber origin andthe amylose or amylopectin fractions thereof. The selected starch in theform of an aqueous slurry, at concentrations up to about 35% by weightsolids, is usually liquefied, by gelatinization or treatment with aliquefying enzyme such as bacterial alpha-amylase enzyme, and thensubjected to treatment with a glycosyltransferase to form thecyclodextrins. The amount of individual alpha-, beta-, andgamma-cyclodextrin formed will vary depending on the selected starch,selected glycosyltransferase and processing conditions. Precipitationand separation of the individual cyclodextrins are described in theliterature using solvent systems, inclusion compounds such astrichloroethylene and non-solvent systems using selected ion exchangeresins. Each of the cyclodextrins as well as mixtures thereof iscommercially available. Beta-cyclodextrin is by far the most widely usedform and is known for use in the production of pharmaceuticals andfoods.

[0018] The property of cyclodextrin molecules that makes them useful forthe present invention is that the molecule has an apolar, hydrophobiccavity which can contain hydrophobic molecules called guest molecules(or the hydrophobic portions of amphiphilic molecules) of appropriatesizes to fit inside the cavity and thus form inclusion complexes. Onewould therefore be led to believe that polar solvents would not have asufficient affinity for the cavity and would not displace the morehydrophobic guests. In the search for a compatible, nondestructive,liquid or meltable carrier for the cyclodextrin complexes it has beenfound that most polar solvents, e.g., the hydroxy and polyhydroxysolvents, e.g., low molecular weight alcohol, ethylene glycol,1,2-propanediol, glycerol and molten sorbitol, at least partiallydecompose the inclusion complexes and release some of the guestmolecules. Surprisingly, it is now found that some liquid or meltablesolids, as described hereinafter, can be used to make pumpable, fluidslurries of cyclodextrin complexes at typical process temperatures,e.g., at about 100-120° C. or lower, without decomposing thecyclodextrin complexes.

[0019] Because of this property of the cyclodextrin to form complexeswith hydrophobic species, hydrophobic moieties of associative thickenerscan bind (get capped) with CDs. The binding of cyclodextrin compoundswith the hydrophobic moieties of associative thickeners disrupts theintermolecular hydrophobic associations and causes a suppression of theviscosity of an aqueous solution containing the associative thickener.The cyclodextrin compounds can then be readily dissociated ordecomplexed from the associative thickener by the addition of anothermaterial which has a greater affinity for the cyclodextrin or bydilution with water.

[0020] The beta-cyclodextrin and its ethoxylated and propoxylatedderivatives are useful in latex paint formulation for achieving avariety of effects, such as for example: to permit the preparation andsupply of a low viscosity, high solids solution of the thickener withoutthe use of viscosity suppressing solvent; improving the ease ofincorporating hydrophobically modified associative thickeners, havingmarginal solubility in water, into aqueous systems; to reduce theviscosity drop of associative thickeners containing formulations uponthe addition of colorants or surfactants to the formulation; to improvethe efficiency of the associative thickener itself, thus reducing thethickeners required to reach a given paint viscosity; to reduce foamingin a paint, with or without an associative thickener, which isespecially desirable when the paint is to be applied by a roller; and toreduce the color development problems caused by surfactants in someformulations.

[0021] Materials that have an affinity for the cyclodextrin and thatcause the decomplexing or desorbing of the cyclodextrin from thehydrophobically modified polymers are described in U.S. Pat. Nos.5,627,232, 5,629,373, 5,914,373 and WO 01/12712 and U.S. Pat. Nos.4,288,639, 4,354,956, 4,354,956, 4,411,819, 4,673,518, 4,904,466, 5,728,895, 5,880,222, 5,916,935, and 6,057,388 and WO 01/2712 are surfactants(i.e., nonionic, cationic, and anionic). These surfactants are readilyavailable in latex formulations. Other solvents that have an affinityfor cyclodextrin are hydroxyl-containing materials such as alcohols.Ethanol is a good example of such an alcohol.

[0022] According to the present invention, normally the lower limit ofthe solids content of the hydrophobically modified aminoplast polyethersor non-urethane polymer associative thickeners in the composition is 3%by weight of the composition, preferably 7%, and more preferably 10%.The upper limit of the thickener polymer solid content is 50% by weight,preferably 25% by weight, and more preferably 20% by weight. Generally,the cyclodextrin content lower limit is 0.2% by weight based on thetotal weight of the composition, preferably 0.5% by weight, and morepreferably 0.7% by weight. The upper limit of the cyclodextrin isgenerally 7.0% by weight, preferably 3.0%, by weight, and morepreferably 1.5% by weight or as dictated by the solubility of the givencyclodextrin at a given temperature and pH.

[0023] According to the present invention, in aqueous solutionscontaining low concentrations of hydrophobically modified aminoplastpolyethers or non-urethane polyether associative thickeners, for exampleon the order of about 3% by weight, it was found that the unmodifiedcyclodextrins, including beta-cyclodextrin, are effective viscositysuppressing additives, while in aqueous solutions containing highconcentrations of hydrophobically modified aminoplast polyethers ornon-urethane polyether associative thickeners, for example on the orderof greater than about 10% by weight, it was found that the modifiedcyclodextrins, having increased water solubility on the order of about50 grams per 100 grams water, are preferred.

[0024] In accordance with this invention, the amount of the cyclodextrinspecies needed to form a target solution depends on the type ofhydrophobically modified aminoplast polyethers or non-urethane polyetherassociative thickeners, its concentration in solution and the type ofcyclodextrin used to suppress the solution viscosity. Cyclodextrin orcyclodextrin derivatives having water-solubility greater than 0.1% canbe used to practice the present invention. Examples of water-solublecyclodextrin derivatives include methylated, hydroxyethylated,hydroxypropylated, carboxymethylated, and diaminoethylatedcyclodextrins. The cyclodextrin derivatives can be nonionic, cationicand anionic. Cyclodextrins or cyclodextrin derivatives having highbinding constants for the hydrophobes present in the hydrophobicallymodified polymers are preferred ones as they efficiently lower thesolution viscosity. Other hydrophilic cyclic molecules, such ascalixarenes, having hydrophobic cavity and ability to complex with thehydrophobes of associative thickeners can also be used.

[0025] In accordance with this invention, the hydrophobically modifiedaminoplast polyethers or non-urethane polyether associative thickenerscompositions can be used in film forming coating compositions such aslatex paints, the pigment volume concentration (PVC) of the latex paintcan have a lower limit of 15, preferably 24, and more preferably 35%.The upper limit of the PVC is normally 85, preferably 65%. According tothe jargon of the paint industry, when the latex paint is a high glosspaint, the PVC is from about 15% to about 30%; when the paint is asemi-gloss paint, the PVC is from about 20 to about 35%; and when it isa flat paint, the PVC is from about 40 to a bout 80%. Also, for latexpaints, the ICI viscosity (as measured by ICI cone and plate viscometer)should be above about 1.5 poise at 25° C., for good performance.

[0026] Besides the latex, waterborne latex paint contains pigments,fillers, surfactants, cosolvents, and thickeners. Other additives thatcan be included in paint formulations, for example, are biocides,dispersants, coalescing agents, preservatives, defoamers, and wet-edgeagents

EXAMPLES

[0027] Hydrophobically modified aminoplast polyethers are marketed bySud-Chemie Rheological group Inc. under the trade mark Optiflo® rheologymodifier. Non-urethane polyether type associative commercial thickenersare marketed by Rheox, Inc. and Cognis Corporation under the trade marksRheolateg rheology modifier and DSX rheology modifier respectively.Commercial samples of these products were obtained from these suppliers.They are all nonionic synthetic associative thickeners used in paints toachieve high high-shear viscosity (ICI viscosity), good flow andleveling and desired gloss.

Standard Procedure to Measure the Solution Viscosity Of the AssociativeThickener in the Presence of β-CD

[0028] To 100 g of the polymer solution was added a known amount of β-CDand the resulting mixture mixed. When the β-CD dissolved, the solutionwas placed in a thermostat, set at 25±0.5° C., for 2 hours and then theviscosity was measured using a Brookfield viscometer.

Example 1 Study of the Solution Viscosity of Optiflo® L100 in thePresence of β-Cd

[0029] Optiflo L100 product is a 20% solids solution of ahydrophobically modified aminoplast-polyether (Mw˜86,700; Mn˜17,500)sold by Süd-Chemie Rheologicals Group. Its solution viscosity is˜3000-3500 cps. The exact chemical structure of the polymer(s) presentin Optiflo L100 is not known.

[0030] According to descriptions in U.S. Pat. No. 5,629,373, and5,914,373, aminoplast-polyether copolymers are made by condensationreaction of a polyfunctional aminoplast with a bifunctional polyether inthe presence of an acid catalyst. Aminoplast reagents are condensationproducts of an aldehyde (formaldehyde) with amines, such as melamines,ureas, benzoguanamines, and glycolurils. The hydrophobes areincorporated into the copolymer backbone by coreacting the bifunctionalpolyether and an ethoxylated alkyl/aryl phenol with the aminoplast.

[0031] Note that the commercial aminoplast may contain a small amount ofdimer and oligomeric products and the reaction of the aminoplast withthe polyether and ethoxylated surfactant is random. Hence, a mixture ofproducts is formed when an aminoplast is condensed with a polyether andan ethoxylated surfactant. The reaction mixture could thus containpolymer chains containing pendant as well as terminal hydrophobes.

[0032] It was found that the solution viscosity of Optiflo L100 productgradually decreased with increasing the amount of β-CD. The results areshown below in Table 1. TABLE 1 Amount of β-CD versus solution viscosityof Optiflo L100 rheology modifier Amount (g) of β-CD per 100 g ofOptiflo L100 Solution BF viscosity (cps) 0 3052 0.2 2556 0.4 2212 0.61976 0.8 1880 1.0 1844 1.2 1816 1.4 1660 1.5 1472

[0033] The results show that the hydrophobe present in Optiflo L100complexes with β-CD leading to reduced solution viscosity. In otherwords, Optiflo L100 solution viscosity decreased in the presence of β-CDand could have a solution viscosity of <2000 cps in conjunction with 0.6wt % of β-CD.

Example 2 Study of the Solution Viscosity of DSX-2000 in the Presence ofβ-CD

[0034] DSX-2000 is a 40% solids solution of a nonurethane associativethickener (Mw˜33,000; Mn˜13,000) in a 1:2 butyl carbitol/water mixture.It is available from Cognis Corporation.

[0035] To study the interaction of the polymer present in DSX-2000product with β-CD, the solid polymer was recovered by evaporation ofsolvent. Since DSX-2000 product contains butyl carbitol, the solidpolymer was first isolated by evaporation of solvent at roomtemperature. Then high solids solutions of the isolated polymer weremade by dissolving the appropriate amount of the polymer in water. β-CDwas obtained from Cerestar USA, Inc. (Hammond, Ind.) and used as is. A30.8% solids solution of the polymer in water was made. The viscosity ofthis solution in the presence of various amounts of β-CD was measured.The results are shown in Table 2. TABLE 2 Amount of β-CD versus 30.8%solids solution viscosity of the polymer present in DSX-2000 Amount (g)of β-CD per 136 g of 30.8% solids solution of the DSX-2000 polymerSolution BF viscosity (cps) 0 1424 0.2 1348 0.4 1292 0.6 1260 0.8 12281.0 1216

[0036] As can be seen from above data, the 30% solution Brookfieldviscosity of the DSX-2000 polymer decreased in the presence of β-CD.

What is claimed is:
 1. A composition comprising a) a hydrophobicallymodified aminoplast polyether or a hydrophobically modified non-urethanepolyether product and b) a viscosity suppressing agent selected from thegroup consisting of cyclodextrins and derivatives thereof.
 2. Thecomposition of claim 1, wherein the cyclodextrins are selected from thegroup consisting of alpha (α), beta (β), and gamma (γ) cyclodextrins. 3.The composition of claim 1, wherein the cyclodextrin derivatives areselected from the group consisting of methylated, hydroxyethylated,hydroxypropylated, carboxymethylated, and diaminoethylated cyclodextrins4. The composition of claim 1, wherein the lower limit of the hydrophobetypes has 8 carbons.
 5. The composition of claim 1, wherein the lowerlimit of the hydrophobe types has 10 carbons.
 6. The composition ofclaim 1, wherein the lower limit of the hydrophobe types has 12 carbons.7. The composition of claim 1, wherein the upper limit of the hydrophobetypes has 40 carbons.
 8. The composition of claim 1, wherein the upperlimit of the hydrophobe types has 28 carbons.
 9. The composition ofclaim 1, wherein the upper limit of the hydrophobe types has 18 carbons.10. The composition of claim 1, wherein the lower limit of the solidscontent of the polymer is 3 wt. %.
 11. The composition of claim 1,wherein the lower limit of the solids content of the polymer is 7 wt %.12. The composition of claim 1, wherein the lower limit of the solidscontent of the polymer is 10 wt %.
 13. The composition of claim 1,wherein the upper limit of the solids content of the polymer is 50 wt %.14. The composition of claim 1, wherein the upper limit of the solidscontent of the polymer is 25 wt %.
 15. The composition of claim 1,wherein the upper limit of the solids content of the polymer is 20 wt %.16. The composition of claim 1, wherein the lower limit of thecyclodextrin content is 0.2 wt %.
 17. The composition of claim 1,wherein the lower limit of the cyclodextrin content is 0.5 wt %.
 18. Thecomposition of claim 1, wherein the lower limit of the cyclodextrincontent is 0.7 wt %.
 19. The composition of claim 1, wherein the upperlimit of the cyclodextrin content is 7.0 wt %.
 20. The composition ofclaim 1, wherein the upper limit of the cyclodextrin content is 3.0 wt%.
 21. The composition of claim 1, wherein the upper limit of thecyclodextrin content is 1.5 wt %.
 22. The composition of claim 1,wherein the solids content of the polymer is 20 wt % and thecyclodextrin content is 1.0 wt %.
 23. The composition of claim 1,wherein the solids content of the polymer is 17 wt % and thecyclodextrin content is 3.0 wt %.
 24. A process for preparing thecomposition of claim 1 comprising dry blending a hydrophobicallymodified aminoplast polyether or hydrophobically modified non-urethanepolyethers with cyclodextrin.
 25. The process of claim 24, wherein theblend is heated to fuse the materials together to form a solid mass. 26.The process of claim 24, wherein the cyclodextrin is selected from thegroup consisting of alpha (α), beta (β), and gamma (γ) cyclodextrins andmixtures thereof.
 27. The process of claim 26, wherein the viscositysuppressing agent is selected from the group consisting of methylated,hydroxyethylated, hydroxypropylated, carboxymethylated, anddiaminoethylated cyclodextrins and mixtures thereof.
 28. A method forimproving the incorporation of a thickener of a hydrophobically modifiedaminoplast polyether or hydrophobically modified non-urethane polyetherswith into an aqueous system containing a water-insoluble polymercomprising a) admixing a cyclodextrin or cyclodextrin derivative withsaid thickener in a sufficient amount to effectively complex thethickener so as to keep the viscosity of the admixture in abeyance, b)adding said complexed admixture to said aqueous system containing saidwater-insoluble polymer, and c) adding or providing to said aqueoussystem containing said complexed admixture and said water-insolublepolymer system an effective amount of a compound having an affinity forthe cyclodextrin to decomplex the cyclodextrin from the thickener toincrease the viscosity of the system.
 29. The method of claim 28,wherein the cyclodextrin is selected from the group consisting of alpha(α), beta (β), and gamma (γ) cyclodextrins and mixtures thereof.
 30. Theprocess of claim 29, wherein the cyclodextrin is selected from the groupconsisting of methylated, hydroxyethylated, hydroxypropylated,carboxymethylated, and diaminoethylated cyclodextrins and mixturesthereof.
 31. A paint composition comprising a latex and the compositionof claim
 1. 32. The paint composition of claim 31, wherein the pigmentvolume concentration (PVC) has a lower limit of about 15%.
 33. The paintcomposition of claim 31, wherein the pigment volume concentration (PVC)has a lower limit of about 24%.
 34. The paint composition of claim 31,wherein the pigment volume concentration (PVC) has a lower limit ofabout 35%.
 35. The paint composition of claim 31, wherein the pigmentvolume concentration (PVC) has an upper limit of about 85%.
 36. Thepaint composition of claim 31, wherein the pigment volume concentration(PVC) has an upper limit of about 65%.